Imaging the Photochemistry of Cyclobutanone using Ultrafast Electron Diffraction: Experimental Results

Abstract

We investigated the ultrafast structural dynamics of cyclobutanone following photoexcitation at $\lambda=200$ nm using gas-phase megaelectronvolt ultrafast electron diffraction. Our investigation complements the simulation studies of the same process within this special issue. It provides information about both electronic state population and structural dynamics through well-separable inelastic and elastic electron scattering signatures. We observe the depopulation of the photoexcited S$_2$ state of cyclobutanone with n3s Rydberg character through its inelastic electron scattering signature with a time constant of $(0.29 \pm 0.2)$ ps towards the S$_1$ state. The S$_1$ state population undergoes ring-opening via a Norrish Type-I reaction, likely while passing through a conical intersection with S$_0$. The corresponding structural changes can be tracked by elastic electron scattering signatures. These changes appear with a delay of $(0.14 \pm 0.05)$ ps with respect the initial photoexcitation, which is less than the S$_2$ depopulation time constant. This behavior provides evidence for the ballistic nature of the ring-opening once the S$_1$ state is reached. The resulting biradical species react further within $(1.2 \pm 0.2)$ ps via two rival fragmentation channels yielding ketene and ethylene, or propene and carbon monoxide. Our study showcases both the value of gas-phase ultrafast diffraction studies as an experimental benchmark for nonadiabatic dynamics simulation methods and the limits in the interpretation of such experimental data without comparison to such simulations.